[Show abstract][Hide abstract] ABSTRACT: Adsorption by microorganisms can play a significant role in the fate and transport of metals in natural systems. Surface complexation models (SCMs) have been applied extensively to describe metal adsorption by mesophilic bacteria, and several recent studies have extended this framework to thermophilic bacteria. We conduct acid–base titrations and batch experiments to characterise proton and Cd adsorption onto the thermophilic archaeon Thermococcus zilligii. The experimental data and the derived SCMs indicate that the archaeon displays significantly lower overall sorption site density compared to previously studied thermophilic bacteria such Anoxybacillus flavithermus, Geobacillus stearothermophilus, G. thermocatenulatus, and Thermus thermophilus. The thermophilic bacteria and archaea display lower sorption site densities than the mesophilic microorganisms that have been studied to date, which points to a general pattern of total concentration of cell wall adsorption sites per unit biomass being inversely correlated to growth temperature.
Chemical Geology 04/2010; 273(1-273):82-90. DOI:10.1016/j.chemgeo.2010.02.014 · 3.52 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Acid–base titrations and electrophoretic mobility measurements were conducted on the thermophilic bacteria Anoxybacillus flavithermus and Geobacillus stearothermophilus at two different growth times corresponding to exponential and stationary/death phase. The data showed significant differences between the two investigated growth times for both bacterial species. In stationary/death phase samples, cells were disrupted and their buffering capacity was lower than that of exponential phase cells. For G. stearothermophilus the electrophoretic mobility profiles changed dramatically. Chemical equilibrium models were developed to simultaneously describe the data from the titrations and the electrophoretic mobility measurements. A simple approach was developed to determine confidence intervals for the overall variance between the model and the experimental data, in order to identify statistically significant changes in model fit and thereby select the simplest model that was able to adequately describe each data set. Exponential phase cells of the investigated thermophiles had a higher total site concentration than the average found for mesophilic bacteria (based on a previously published generalised model for the acid–base behaviour of mesophiles), whereas the opposite was true for cells in stationary/death phase. The results of this study indicate that growth phase is an important parameter that can affect ion binding by bacteria, that growth phase should be considered when developing or employing chemical models for bacteria-bearing systems.
[Show abstract][Hide abstract] ABSTRACT: Acid-base functional groups at the surface of Anoxybacillus flavithermus (AF) were assigned from the modeling of batch titration data of bacterial suspensions and compared with those determined from in situ infrared spectroscopic titration analysis. The computer program FITMOD was used to generate a two-site Donnan model (site 1: pKa = 3.26, wet concn = 2.46 x 10(-4) mol g(-1); site 2: pKa = 6.12, wet concn = 6.55 x 10(-5) mol g(-1)), which was able to describe data for whole exponential phase cells from both batch acid-base titrations at 0.01 M ionic strength and electrophoretic mobility measurements over a range of different pH values and ionic strengths. In agreement with information on the composition of bacterial cell walls and a considerable body of modeling literature, site 1 of the model was assigned to carboxyl groups, and site 2 was assigned to amino groups. pH difference IR spectra acquired by in situ attenuated total reflection infrared (ATR-IR) spectroscopy confirmed the presence of carboxyl groups. The spectra appear to show a carboxyl pKa in the 3.3-4.0 range. Further peaks were assigned to phosphodiester groups, which deprotonated at slightly lower pH. The presence of amino groups could not be confirmed or discounted by IR spectroscopy, but a positively charged group corresponding to site 2 was implicated by electrophoretic mobility data. Carboxyl group speciation over a pH range of 2.3-10.3 at two different ionic strengths was further compared to modeling predictions. While model predictions were strongly influenced by the ionic strength change, pH difference IR data showed no significant change. This meant that modeling predictions agreed reasonably well with the IR data for 0.5 M ionic strength but not for 0.01 M ionic strength.
[Show abstract][Hide abstract] ABSTRACT: Numerous studies have utilized surface complexation theory to model proton adsorption behaviour onto mesophilic bacteria. However, few experiments, to date, have investigated the effects of pH and ionic strength on proton interactions with thermophilic bacteria. In this study, we characterize proton adsorption by the thermophile Anoxybacillus flavithermus by performing acid–base titrations and electrophoretic mobility measurements in NaNO3 (0.001–0.1 M). Equilibrium thermodynamics (Donnan model) were applied to describe the specific chemical reactions that occur at the water–bacteria interface. Acid–base titrations were used to determine deprotonation constants and site concentrations for the important cell wall functional groups, while electrophoretic mobility data were used to further constrain the model. We observe that with increasing pH and ionic strength, the buffering capacity increases and the electrophoretic mobility decreases. We develop a single surface complexation model to describe proton interactions with the cells, both as a function of pH and ionic strength. Based on the model, the acid–base properties of the cell wall of A. flavithermus can best be characterized by invoking three distinct types of cell wall functional groups, with pKa values of 4.94, 6.85, and 7.85, and site concentrations of 5.33, 1.79, and 1.42 × 10−4 moles per gram of dry bacteria, respectively. A. flavithermus imparts less buffering capacity than pure mesophilic bacteria studied to date because the thermophile possesses a lower total site density (8.54 × 10−4 moles per dry gram bacteria).